Process for dyeing or printing fiber materials containing nh-groups

ABSTRACT

Process for dyeing or printing NH-containing fibers with reactive dyestuffs containing at least one group reactive to the NH-group and more than 1 sulfonic acid group comprising adding as surface active compounds aminoxides with at least eight carbon atoms in one and the same radical.

United States Patent I-Ielmut Klrsehnek; Dietrich Hildebrand, both 01Leverkusen; UdO-Willfliedlitflllicks, Cologne Stemmheim; GerhardMelenieverkusen- Rheindorf; Mathieu Quaedvlleg, Opladen,

[72] Inventors all of Germany [21] Appl. No. 734,537

[22] Filed June 5, 1968 [45] Patented Dec. 21, 1971 [73] AssigneeFarbenlabriken Bayer Aktlengesellsehait Leverkusen, Germany [32]Priorities June 15, 1967 [3 3] Germany Apr. 17, 1968,.Germany, No. 1 1769 172.4

[54] PROCESS FOR DYEING 0R PRINTING FIBER MATERIALS CONTAININGNII-GROUPS 12 Claims, No Drawings [52] US. Cl 8/54, 8/1 B,8/1 D, 8/1E,8/1 L, 8/1UA,8/1T,8/1XA, 8/21 A, 8/21 B, 8/88, 8/39, 8/40, 8/163, 8/169,8/41 B [51] Int. Cl C09b12/00, D06p 3/14 [50] Field of Search 8/l.2, 85,88, 21 54 [56] Reierences Cited UNITED STATES PATENTS 3,098,794 7/1963Dohr et a1. 260/577 X 3,206,451 9/1965 Benz et a1. 260/153 PrimaryExaminer-George F. Lesmes Assistant Examiner Patricia C. IvesAuorney--P1um1ey,Tyner & Sandt ABSTRACT: Process for dyeing or printingNH-containing fibers with reactive dyestuffs containing at least onegroup reactive to the NH-group and more than 1 sulfonic acid groupcomprising adding as surface active compounds aminoxides with at leasteight carbon atoms in one and the same radical.

PROCESS FOR DYEING R PRINTING FIBER MATERIALS CONTAINING NII-GROUPS Thepresent invention relates to a process for dyeing and printing fibermaterials containing NI-I-groups with dyestuffs which contain at leastone group capable of reacting with the fiber materials containingNI-I-groups and which contain more than one sulfonic acid group. Moreparticularly it concerns a process wherein the dyeing and printing iscarried out in the presence of aminoxides which contain at least eightcarbon atoms.

Suitable aminoxides are primarily compounds which contain eight tocarbon atoms in one and the same hydrocarbon radical. Examples are thefollowing aminoxides with only one aminoxide group:

N,N-dimethyl-N-dodecylaminoxide N,N-dimethyl-N-hexadecylaminoxideN,N-dimethyl-N-octadecenyl-aminoxide N,N-dibutyl-N-dodecylaminoxideN-methyl-N-cyclohexyl-N-dodecylaminoxideN,N-dimethyl-N-(dodecanoylamino-methyl)-aminoxideN,N-diethyl-N-(B-octadecenoylamino-ethyl)-aminoxideN,N-dimethyl-N-(a-octadecanoylamino-propyl)-aminoxideN,N-dimethyl-N-[a-(N-octadccyl-carbaminyl)-aminopropyl]-aminoxideN,N-dimethyl-N-(a-octadecyl-sulphonylamino-propyl)- aminoxideN,N-dimethyl-N-(a-oleoylamino-propyl)-aminoxideN-methyl-N,N-bis-[a-(octadecanoylamino)-propyllaminoxideN-methyl-N,N-bis-[a-(dodecanoylamino)-propyl]-aminoxideN-methyl-N,N-bis-[a-(oleoylamino)-propyl]-aminoxide N,N-dimethyl-N(B-octadecyloxy-ethyl)-aminoxideN-methyl-N-B-hydroxyethyl-N-[a-(octadecanoylamino)- propyl]-aminoxideN-methyl-N-fi-hydroxyethylN[a-(oleoylamino)-propyl]- aminoxideN-methyl-N-[a-(octadecanoylamino)-propyl]-N-[B-(octadecanoyloxy)-ethyl]-aminoxideN,N-dimethyl-N-[B-(N'-octadecylcarbaminyl)-hydroxyethyll-aminoxideN,N-bis-(B-hydroxyethyl)-N-stearylaminoxideN-methyl-N-benzyl-N-dodecylaminoxideN,N-dimethyl-N-(2-oxy-5-tert.butyl-benzyl)-aminoxideN,N-dimethyl-N-[(Z-oxy-naphthyl-l-)-methyl]-aminoxide N,N-dimethyl-N-(4-dodecyl-phenyl )-aminoxideN,N-dimethyl-N-(4-dodecanoyl-phenyl)-aminoxideN-dodecyl-morpholine-N-oxide N-hexadecyl-morpholine-N-oxideN-dodecyl-piperidine-N-oxide N-hexadecyl-piperidine-N-oxideN-dodecyl-imidazole-N-oxide N-dodecyl-benzimidazole-N-oxideN-I-(B-hydroxethyl)-2-octadecyl-imidazoline-N-oxidel-(B-octadecanoylamino-ethyl )-2-octadecy|-imidazoline- N-oxide.

There may further be mentioned the following aminoxides which containseveral aminoxide groups:

N,N-dimethyl-N-propyl-N'-decyl-ethylene-diamine-N,N'- dioxideN,N-diethyl-N'-methyl-N'-octadecyl-ethylene-diamine-N,N '-dioxideN,N,N'-triethyl-N'-dodecyl-ethylene-diamine-N,N'-dioxideN,N,N'-tripropyl-N'-tetradecyl-ethylene-diamine-N,N'- dioxideN,N,N'-trimethyl-N'-decyl-l ,B-propylene-diamine-N,N'- dioxide N,N,N'-trimethyl-N -hexadecyll ,3-propylene-diamine- N,N-dioxideN,N-diethyl-N'-methyl-N'-dodecyl-l,3- propylene-diamine-N,N-dioxideN,N,N '-tris-(B-hydroxyethyl)-N '-octadecyl- I,3-propylenediamine-N,N-dioxideN,N,N,N-tetramethyl-aminoundecylamine-N,N-dioxideN,N,N,N'-tetramethyl-aminomethyl-stearylamine-N,N'- dioxide2,5-dihydroxy-l ,4-bis-(dimethylaminomethyl)-benzene- N,N-dioxide2,2-bis-[4'-hydroxy-3'-(dimethylaminoxide-methyl)-phenyl]-propane Adipicacid-di-(fil -oxide-imidazolinel -yl-ethyl )-ester, and, moreover, theaminoxides which are obtained when in high-molecular compoundscontaining several tertiary amino groups-e.g. in condensation productsobtained from N-B- hydroxyethyl-N-a-aminopropyl-N-methylamine orbis-(aaminopropyl)-methyI-amine and adipic acid or sebacic acid or theiresters; in copolymersobtained from 2-vinyl-pyridine and ethylene,propylene or dodecyl acrylate; in polyureas obtained frombis-(a-aminopropyl)-methylamine and hexamethylene diisocyanate ortoluidene diisocyanate; in polyurethanes obtained frombis-(B-hydroxyethyl)-methylamine or N-B-hydroxyethyl-N-a-aminopropyl-N-methylamine and hexamethylenediisocyanate or toluidine diisocyanate; in reaction products of a,B-unsaturated carboxylic acids, such as acrylic acid, methacrylic acid,crotonic acid and maleic acid or their esters, withbis-(a-aminopropyl)-methylamine; and in reaction products of epoxides,such as epichlorohydrin, butylene dioxide and diglycidyl-ethylene glycolether, with bis-(aaminopropyl)-methylamine-the tertiary amino groups arecompletely converted into aminoxide groups in known manner by means ofhydrogen peroxide.

Furthermore, there may also be used those aminoxides which containpolyglycol ether groups, in addition to one aminoxide group or severalaminoxide groups. Examples are the following compounds:

l-(dimethylamino-N-oxide )-3 ,6,9-trioxa-l l-(4 '-nonylphenoxy)-undecanel-(dimethylamino-N-oxide)-2-hydroxy-4-hexadecanel-(dimethylamino-N-oxide)-3,6,9-trioxa-heneicosane1-(dimethylamino-N-oxide)-4,7,10,13 ,1 6-penta-oxa-l9-thiahentriacontane N-monoxides of the reaction products of 3-200 molesethylene oxide with I mole stearylamine, and N,N'-dioxides of thereaction products of 5-200 moles ethylene oxide with 1 mole9-aminostearylamine or 9-(aminomethyl)-stearylamine.

Finally, those aminoxides which contain a basic nitrogen atom or severalbasic nitrogen atoms, in addition to one aminoxide group or severalaminoxide groups, are also suitable for the process of the presentinvention. Examples are the following compounds:

N-rnethyl-N-octadecyl-N-[3-(di-p-hydroxyethylamino)- propyll-aminoxideN-methyl-N-octadecyl-N-(3-dimethylamino)-propylaminoxideN-methyl-N-octadecyl-N-[ 3-( a-aminopropylamino)- propyl]-aminoxide, andthose aminoxides which are obtained when in the abovementioned compoundscontaining several tertiary amino groups, e.g. condensation products,copolymers, polyureas, polyurethanes, conversion products and reactionproducts, only part of the tertiary amino groups is converted intoaminoxide groups.

The aminoxides to be used according to the invention are obtainable in amanner known as such by oxidation of the corresponding tertiary aminespreferably with hydrogen peroxide or peracids (see Houben-Weyl Methodender organischen Chemie," vol. XI/2, p. 192-200, 4th edition, 1958).

The necessary amounts of aminoxides can easily be established in everycase by preliminary experiments; in general, amounts of 0.2-3 percent,referred to the weight of the fiber materials containing NI-I-groups,which are to be dyed or printed, will prove sufficient.

It has often proved to be of advantage, for example if precipitationsoccur to use, in addition to the aminoxides, also dispersing agents,expediently those of a nonionic type, such as e.g. the reaction productsof 6-200 moles ethylene oxide with 1 mole fatty alcohol, fatty acid orfatty acid amide and the reaction products of such polyglycol etherswith alkylating or acylating agents, such as dimethyl 'or diethylsulfate or acetic acid or methyl isocyanate. Also in these cases, theex;

pedient amounts of dispersing agents can easily be established bypreliminary experiments; in general, amounts of about 20-100 parts byweight per 100 parts by weight aminoxide will suffice.

Fiber materials containing NH-groups, which are suitable for the processaccording to the invention are, in the first instance, wool, silk andthose synthetic fiber materials which are based on poly-e-caprolactam,polyheramethylene-diamine adipate or w-amino-undecanic acid. The fiberscontaining Nil-groups may be present in mixture with other fibers, forexample, in mixture with fibers of natural or regenerated cellulose,cellulose triacetate, polyacrylonitrile, polyurethanes, polyestersobtained form terephthalic acid and ethylene glycol, or polyestersobtained from terephthalic acid and 1,4- bis-hydroxymethyl-cyclohexane.

Numerous dyestuffs are known, which contain at least one group capableof reacting with the fiber materials containing NH-groups and containmore than one sulfonic acid group; suitable groups which are capable ofreacting with fiber materials containing NHgroups are, for example:halotriazine, such as fluoro-, chloroor bromo-triazine, halopyrimidine,such as fiuoro-, chloroor bromo-pyrimidine, haloquinoxaline-carbonyl,halophthalazine-carbonyl, vinylsulfone fi-hydroxyethyl-sulfone ester,methylsulfonyl-triazine, methylsulfonyl-pyrimidine,methysulfonyl-benzothiazole, fiuorobenzothiazole,B-hydroxyethyl-suIfonamide ester, )8- hydroxy-ethyl-sulfon-alkylaminoester, a-bromoacrylorl, fichloropropionyl, B-chloroacetyl,B-phenylsulfonylpropionyl, halopyridazone alkyl, 2-chloroben2othiazolesulfonyl alkylsulfonyl-pyrimidine, ammonium triazine and acryloyl groupsor groups which can be converted into these groups.

Reference be made in this context to the following publications in whichdyestuffs are described, which contain at least one group capable ofreacting with fiber materials containing Nil-groups and contain morethan one sulfonic acid group: Angewandte Chemie 1961, pages 125-136;1964, pages 423-431; American Dyestuff Reporter 1961, pages 505-515;British Pat. Specifications Nos. 733-471, 916,094, 902,618, 1,002,648,1,000,801, 1,067,876, 797,946, 798,121, 822,047, 837,750, 887,588,995,791 and 989,192; French Pat. Specification Nos. 1,427,781 and1,466,567; Swiss Pat. Specification No. 364,062; and US. Pat.Specification No. 2,657,205. The classes of dyestuffs illustrated arereactive dyestuffs where the chromophore therein includes vat dyestuffs,acid dyestuffs, water soluble or insoluble dyestuffs especially azo andmetallized azo dyestuffs (including mono and poly azo dyestuffs);

nitro; triphenylmethane; azaporphin especially phthalocyanines,metallized phthalocyanines; azomethine; benzanthrone; dibenzanthrone;polycyclic condensation products of dibenzanthrone; polynuclear quinonesespecially anthraquinones; oxazine, dioxazine.

The dyeing or printing of the fiber materials containing NH- groups withthe dyestuffs concerned in the presence of the aminoxides is expedientlycarried out in a weakly acidic bath or with weakly acidic printingpastes under the conditions of temperature usually applied for reactivedyestuffs.

With the aid of the process according to the invention it is possible toachieve dyeings or prints of outstanding levelness and a high degree offixation on fiber materials containing NH-groups. This is also true whendifferences in the affinity to the dyestuff used exist in the fibermaterial, as is the case, for example, with wool fibers. bevel dyeingsare also obtained with mixtures of dyestuffs which exhibit substantialdiffcrences with regard to their reactivity to the fiber material. Eventhe reactive dyestuffs of the phthalocyanine series, which contain, onaverage, 1-2 sulfonic acid groups per molecule and have hitherto beendifiicult to level, yield uniform dyeings in the process according tothe invention.

It is known that the dyeing or printing of fiber materials containingNHl-groups with dyestuffs which contain at least one group capable ofreacting with the fiber material and contain more than one sulfonic acidgroup, encounters substantial difficulties. The auxiliaries which havehitherto been proposed for overcoming these difficulties do not exhibitthe advantageous effects described above to the same extent.

The parts given in the following examples are parts by weight; theconstitutions of the dyestuffs characterized by (l) to (XlV) areillustrated in the survey at the end of the examples.

EXAMPLE 1 One hundred parts of loose wool tending to yield tippy dyeingsare introduced at 40 C. into a dyebath which is composed as follows:

5000 parts of water 3 parts of 60 percent acetic acid 5 parts ofanhydrous sodium sulfate 0.5 parts of the reaction product of 19 molesethylene oxide with 1 mole oleyl alcohol 1.2 parts of the 50 percentaqueous solution of a highmolecular aminoxide described below 2 parts ofa mixture of equal parts of the dyestuffs (l) and The dyebath is broughtto the boil within 45 minutes and held at this temperature for 75minutes. The loose wool is subsequently withdrawn from the bath, rinsedin the usual manner with water and dried. A level violet dyeing isobtained,

The 50 percent aqueous solution of the high-molecular aminoxide usedabove was prepared in the following manner:

A mixture of 174 parts adipic acid methyl ester and 143 partsN-bis-(a-aminopropyl)-methylamine is heated with stirring at 170-180' C.for 1% hours, subsequently cooled to C., then mixed with 15 parts aceticacid anhydride and stirred at 130 C. for a further 30 minutes. Onehundred parts of the polyamide so obtained are dissolved in 100 partsethanol, mixed with parts of 30 percent hydrogen peroxide and heated at50-60 C. for 5 hours. The bulk of the excess hydrogen peroxide is thendestroyed by introducing a platinum sheet, and the residual amount bythe dropwise addition of a 25 percent solution of sodium platinum sheet,and the residual amount by the dropwise addition of a 25 percentsolution of sodium sulfite. The precipitated sodium sulfate is filteredoff, the filtrate is concentrated by evaporation, and the residue mixedwith a sufficient amount of water that the solids content of theresultant aqueous solution amounts to 50 percent EXAMPLE 2 The procedureis as described in example 1, but with the use of a dyebath whichcontains, instead of 1.2 parts of the stated 50 percent aqueous solutionof the high-molecular aminoxide and the stated dyestuff mixture, 0.8parts of the aminoxide of the formula and 2.1 parts of a mixture ofequal parts of the dyestuffs (l), (111) and (IV). A level brown dyeingis obtained.

EXAMPLE 3 The procedure is as described in example 1, but with the useof a dyebath which contains, instead of 1.2 parts of the stated 50percent aqueou solution of the high-molecular aminoxide and the stateddyestufi' mixture, 1.25 parts of the aminoxide of the formula and 2parts of a mixture of equal parts of the dyestuffs (ill) and (IV). Alevel vivid green dyeing is obtained.

EXAMPLE 4 The procedure is as described in example 1, but with the useof a dyebath which contains, instead of the stated 50 percent aqueoussolution of the high-molecular aminoxide and the stated dyestuffmixture, l.l parts of the aminoxide of the formula ((1111 mm mm" (Ill;((lllzht (ill; N

and 2.l parts of a mixture of equal parts of the dyestuffs (l), (Ill)and (V). A level brown dyeing is obtained.

EXAMPLE 5 One hundred parts of woolen knitting yam are introduced at 40C. into a dyebath which is composed as follows: 4000 parts of water 3parts of 60 percent acetic acid 5 parts of anhydrous sodium sulfate 0.25parts of the reaction product of 19 moles ethylene oxide with 1 moleoleyl alcohol,

0.25 parts of the aminoxide of the formula parts of the dyestuff (Ill).

The dyebath is heated to boiling temperature within 45 minutes and heldat this temperature for 60 minutes. The knitting yarn is subsequentlyrinsed and dried in the usual manner. A level yellow dyeing is obtained.

A level yellow dyeing is also obtained by using a dyebath whichcontains, instead of 0.25 parts of the stated aminoxide, 0.35 parts ofthe aminoxide of the formula or 0.35 parts of the aminoxide of theformula EXAMPLE 6 The procedure is as described in example 5, but withthe use of a dyebath which contains, instead of 0.25 parts of the statedaminoxide and 2 parts of the dyestuff (Ill), 0.2 parts of the aminoxideof the formula and 2 parts of the dyestuff (l). A vivid level red dyeingis obtained.

and 2 parts of the dyestuff (Vll). A level red dyeing is obtained.

EXAMPLE 8 The procedure is as described in example 5, but with the useof a dyebath which contains, instead of 0.25 parts of the statedaminoxide and 2 parts of the dyestuff (lll), 0.3 parts of the aminoxideof the formula and 2 parts of a mixture of equal parts of the dyestuffs(l) and (III). A level orange dyeing is obtained.

EXAMPLE 9 The procedure is as described in example 5, but with the useof a dyebath which contains, instead of 0.25 parts of the statedaminoxide and 2 parts of the dyestuff (Ill), 0.25 parts of the aminoxideof the formula and 2 parts of the dyestuff (II). A vivid level bluedyeing is obtained.

EXAMPLE 10 One hundred parts of wool fabric are introduced at 40 C. intoa dyebath which is composed as follows: 5000 pans of water 3 parts of 60percent acetic acid 5 parts of anhydrous sodium sulfate 0.5 parts of thereaction product of 19 moles ethylene oxide with 1 mole oleyl alcohol0.4 parts of the aminoxide of the formula /Cl 1 Cm- (Cums-C0--NII 0m);-N

U Ulla 2 parts of the dyestufi' (IV).

The dyebath is heated to C. within 30 minutes, held at this temperaturefor 30 minutes, then heated to boiling temperature and held at thistemperature for 30 minutes. The wool fabric is subsequently rinsed anddried in the usual manner. A level turquoise dyeing is obtained.

EXAMPLE l l The procedure is as described in example 10, but with theuse of a dyebath which contains, instead of 0.4 parts of the statedaminoxide and 2 parts of the dyestuff (IV), 0.65 parts of the aminoxideof the formula and 2 parts of the dyestuff (II). A vivid level bluedyeing is obtained.

EXAMPLE 12 The procedure is as described in example 10, but with the useof a dyebath which contains, instead of 0.5 parts of the reactionproduct of 19 moles ethylene oxide with 1 mole oleyl alcohol, 0.75 partsof this product and, instead of 0.4 pans of the stated aminoxide and 2parts of the dyestuff (IV), 0.35 parts of the aminoxide of the formulaand 2 parts of a mixture of 1 part of the dyestuff (VI) and 3 parts ofthe dyestuff (ll). A level dark-blue dyeing is obtained.

EXAMPLE 13 One hundred parts of a wool top yarn wound on cheeses areintroduced at 40 C. into a dyebath which is composed as follows:

2000 parts of water 3 parts of 60 percent acetic acid parts of anhydroussodium sulfate 1.5 parts of the aminoxide of the formula 2 parts of thedyestuff V l).

The dyebath is heated to 106 C. within 30 minutes and held at thistemperature for 30 minutes. The wool top yarn is subsequently rinsed anddried in the usual manner. A level Bordeaux dyeing is obtained.

EXAMPLE l4 One hundred parts of a knitted fabric made of polyamide basedon polyhexamethylene-diamine adipate are introduced into a dyebath whichis composed as follows:

4000 parts of water 2 parts of 60 percent acetic acid 0.5 parts of thereaction product of 19 moles ethylene oxide with 1 mole oleyl alcohol0.35 parts of the aminoxide of the formula 2 parts of the dyestuff VI).

The dyebath is heated to boiling temperature within 45 minutes and heldat this temperature for 60 minutes. The knitted fabric is subsequentlyrinsed and dried in the usual manner. A level Bordeaux dyeing isobtained.

EXAMPLE 15 One hundred parts of yarn of natural silk are introduced at40 C. into a dyebath which is composed as follows: 3000 parts of water2.5 parts of 60 percent acetic acid 0.5 parts of the reaction product of19 moles ethylene oxide with 1 mole oleyl alcohol The dyebath is heatedto 95 C. within 45 minutes and held at this temperature for 60 minutes.The yarn is subsequently rinsed and dried in the usual manner. A levelblue dyeing is obtained.

EXAMPLE l6 Woolen combed material is printed according to the Vigoureuxprinting process with a paste which is composed as follows:

20 parts of the dyestuff (l) 60 parts urea 5 parts of the reactionproduct of 19 moles ethylene oxide with 1 mole oleyl alcohol l0 parts ofthe aminoxide of the formula ulnxolim on, co Nll cum om 15 parts of 60percent acetic acid 8 parts of a thickening agent based on carob beanflour 882 parts of water.

After printing, the combed material is steamed at l00 C. for 1 hour,then rinsed with cold and hot water and finished in the usual manner. Alevel red print is obtained.

EXAMPLE 17 One hundred parts of loose wool tending to yield tippydyeings are introduced at C. into a dyebath which is com posed asfollows:

4000 parts of water 3 parts of 60 percent acetic acid 5 parts ofanhydrous sodium sulfate 2 parts of the dyestuff (VIII).

The dyebath is brought to the boil within minutes and held at thistemperature for 60 minutes. The loose wool is subsequently withdrawnfrom the bath, rinsed in the usual manner with water and dried. A levelyellow dyeing is obtained.

EXAMPLE 18 One hundred parts of woolen combed material are introduced at40 C. into a dyebath which is composed as follows:

4000 parts of water 3 parts of 60 percent acetic acid 5 parts ofanhydrous sodium sulfate 0.5 parts of the reaction product of 19 molesethylene oxide with 1 mole oleyl alcohol 0.5 parts of the aminoxide ofthe formula 2 parts of the dyestuff (IX).

The dyebath is heated to boiling temperature within 45 minutes and heldat this temperature for 60 minutes. The combed material is subsequentlywithdrawn from the bath rinsed in the usual manner and dried. A levelblue dyeing with neutral shade is obtained.

EXAMPLE l9 One hundred parts of woolen knitting yarn are introduced at40 C. into a dyebath which is composed as follows: 4000 parts of water 3parts of 60 percent acetic acid parts of anhydrous sodium sulfate 0.25parts of the reaction product of 19 moles ethylene oxide with 1 moleoleyl alcohol 0.25 parts of the aminoxide of the formula /C Usclla(c.ui)lfl o0-Nu-(CH2)3N l O CH2CH2OH 2 parts of the dyestuff (X).

The dyebath is heated to 70 C., held at this temperature for 45 minutesand then heated to boiling temperature and held at 25 this temperaturefor minutes. The knitting yarn is subsequently rinsed and dried in theusual manner. A level orange dyeing is obtained.

EXAMPLE The procedure is as described in example 19 but with the use ofa dyebath which contains, instead of the one part of the dyestuff (X),two parts of the dyestuff (XI). A level red dyeing is obtained.

EXAMPLE 2] One hundred parts of a wool top yarn wound on cheeses areintroduced at C. into a dyebath which is composed as follows:

2000 parts of water 3 parts of 60 percent acetic acid 5 parts ofanhydrous sodiumsulfate 0.5 parts of the reaction product of l9 molesethylene oxide with 1 mole oleyl alcohol 0.25 parts of the aminoxide ofthe formula i 2 parts of the dyestufi (XII). The dyebath is heated tothe boil within minutes and held at this temperature for minutes. Thewool top yarn is subsequently rinsed and dried in the usual manner. Alevel ruby red dyeing is obtained.

EXAMPLE 22 One hundred parts of a woolen knitted fabric are introducedat 40 C. into a dyebath which is composed as follows:

20 5000 parts of water 3 parts of 60 percent acetic acid 5 parts ofanhydrous sodium sulfate 0.5 parts of the reaction product of 19 molesethylene oxide with 1 mole oleyl alcohol 0.5 parts of the aminoxide ofthe formula 2 parts of the dyestuff (Kill).

The dyebath is heated to the boil within 45 minutes and held at thistemperature for 60 minutes. The wool fabric is subsequently rinsed anddried in the usual manner. A level greenish blue dyeing is obtained.

EXAMPLE 23 When dyeing I00 parts of a wool fabric in the same manner asdescribed in example 22, replacing however dyestuff (Xlll) by dyestuff(XIV), a level red dyeing is obtained.

Survey of the dyestufi's used in the examples SOaNn DyestufiConstitution x11 Naoa s l OH N: N 01 l I p I fiam om gb N3030 (XIII)Nr-I,

A s OaNa 1 NaO3S- (71 N n l i O N N w HQ 11 N I (X I m 1 1 s N Cl-fiwarn. fi N F NBOZS We claim: group consisting of NH-CONH(CH,) CONl-ll. Aprocess for dyeing or printing fibers containing NH- groups comprisingapplying to said fibers, dyestuffs containing at least one group capableof reacting with fiber materials containing NH-groups and containingmore than one sulfonic acid group, and an aminoxide which contains atleast eight carbon atoms.

2. Process according to claim 1 wherein nonionic dispersing agents arealso used.

3. Process according to claim 2, wherein that as nonionic dispersingagents are used the ethoxylation products of fatty alcohols, fatty acidsor fatty acid amides respectively, their alkylation or acylationproducts.

4. The process according to claim 2 wherein the nonionic dispersingagents are selected from the group consisting of the ethoxylationproducts of fatty alcohols, fatty acids or fatty amides and theiralkylation or acylation products.

5. The process according to claim 1 wherein the aminoxides are presentin a quantity of 0.2 to 3 percent based on the weight of the fibermaterials.

6. Process according to claim 1 wherein the aminoxides contain eight tocarbon atoms in one and the same hydrocarbon radical.

7. Process according to claim 6, wherein the C,--C,, hydrocarbon radicalis a C C alkyl or C C, alkenyl radical.

8. Process according to claim 7 wherein the aminoxides containing a C -C-alkyl radical are aminoxides of the formula wherein R denotes a C C,alkyl or C,,-C -alkenyl radical; A is a direct C-Nbond or a memberselected from the or forms together with R a morpholine ring.

11. Process according to claim 8 wherein R denotes a C -c alkyl or C,alkenyl radical;

R is methyl; and

12. Process according to claim 8 wherein R denotes a C C,,,alkylradical;

R and R are methyl.

UNITED STATES PATENT OFFICE CERTIFIQATE or cohhhorioh Patent No.3,628,905 Dated December 21, 1971 I nventofls) Helmut Kirschnek, et a1.

It is certified that error appears in the above-identified patent andthat said Letters Patent are hereby corrected as shown below: Column ILine Error 1 22 should be b 1 23 should be ,2--

1 25 should be a 1 27 should be 1-.

1 28 should be a -o 1 3.0 should be zm 1 32 should be l 34 should be 5,

1 35 W should be y--.

l 38 should be i 2 9 should be I (both occurrences) o 2 13 should be a 2l6 should be ---J---.

2 20 should be g -o 2 22 should be J- -a.

2 so should be X- -Q -1- F ORM F'O-IOSO (10-69) USCOMM- DC 60376-P69 U5.GOVERNMENT PRINTING OFFICE: 969 0-366-334 UNITED STATES PATENT 0mmCERTIFECATE @F QURECTlQN Patent No, 3,628,905 Dated December 21, 1971lnventor(s) Helmut Kirschnek, et al- It is certified that error appearsin the above-identified patent and that said Letters Patent are herebycorrected as shown below:

Column Lihe Error 2 45 "(di--p" should be --(diB--- 3 8"polyheramethylene" should be I I ---polyhexamethylene 3 13 l "form"should be ---from---..

3 27 -"v -bromoacrylorl" should be v --v --bromoacryloyl-.

3 39 "733-471" should be ---733,47l--- 4 29 should be 1-.

4 30 "l70l80' should be --l70l80--.

4 38 "platinum sheet, the residual amount by the dropwise addition of a25% solution of sodium" should be deleted.

5 Ex 4 (CH -CH -O) H in the 2 formula "N 1 should be 5 1 -69 ORM PO oU5COMM-DC 60376-P69 I a 1.5. GOVERNMENT PRINTING OFFCEZ 959 0"365334UNTTEn STATES PATENT @FFKCE CERTIFECATE UT QQRREQTWN Patent No.3,628,905 Dated December 21, 1.971

Ihventofls) Helmut Kirschnek, et a1.

. It is certified that error appears in the above-identified patent andthat said Letters Patent are hereby corrected as shown below:

Column Line Error 5 37 Beforethe first worfi in the sentence I "parts,insert the number --2--.

7 1st Insert hyphens to read formula 3 c H (cH c0-Ns-(cH g 11 formula"NaO S" should be --=-==-SO Na (VII) ll formula "NaO should be -=-NaOS---.

. l3 formula "NaO O" should be ---NaO S--= (XII) b180 5 l3 formula (XII)should be F ORM PO-105O (10-69) USCOMM'DC 60376-F69 W U. S. GOVERNMENTPRINTING OFFICE: I969 0-366-334 FORM PO-IOSO (10-69) PAGE 4 UNITED.STATES PATENT GFFHQE 4 CERTIFICATE ,QF QUR EQEN Patent No- 3,523,905Dated December 21, 197].

Inventor(s) Helmut Kirschnek, 'et al.

I It is certified that error appears in the above-identified patent andthat said Letters Patent are hereby corrected as shown below:

Column Line Error l3 Claim In the defin ition 0:? R "-(CH CH H," 8should be (CH CH O) H,=--;

in the definition of R (CH CH O) 2;"

should be -(CH CH O) H-=----, 14 cleim In the definition of R (CH CH O)21," i 10 should be -(CH CH O) H,-=--;

In the definition of R (ch cfi o) 11" should be -(CH CH 0) H----,

" l3 Clgim "Process according to that as no should be ---Processaccording to as Signed and sealed this 8th day of October 1974,

(stir Attest:

MCCOY M. GIBSON JR. C, MARSHALL DANN Attesting Officer Commissioner ofPatents USCOMM'DC 6Q375-P59 U.S. GOVERNMENT PRlNTiNG OFFICE I9690-386-334

2. Process according to claim 1 wherein nonionic dispersing agents arealso used.
 3. Process according to claim 2, wherein that as nonionicdispersing agents are used the ethoxylation products of fatty alcohols,fatty acids or fatty acid amides respectively, their alkylation oracylation products.
 4. The process according to claim 2 wherein thenonionic dispersing agents are selected from the group consisting of theethoxylation products of fatty alcohols, fatty acids or fatty amides andtheir alkylation or acylation products.
 5. The process according toclaim 1 wherein the aminoxides are present in a quantity of 0.2 to 3percent based on the weight of the fiber materials.
 6. Process accordingto claim 1 wherein the aminoxides contain eight to 20 carbon atoms inone and the same hydrocarbon radical.
 7. Process according to claim 6,wherein the C8-C20-hydrocarbon radical is a C8-C20-alkyl orC8-C20-alkenyl radical.
 8. Process according to claim 7 wherein theaminoxides containing a C8-C20-alkyl radical are aminoxides of theformula
 9. Process according to claim 8 wherein A is a direct C-N-bond,-NH-CONH-(CH2)3- or -CONH-(CH2)3-.
 10. Process according to claim 8wherein R denotes a C14-C18-alkyl radical; A is a direct C-N-bond; R1denotes methyl, Beta -hydroxyethyl, -(CH2CH2O)3,5H or-(CH2CH2O)14-CH2CH2OH; and R2 is methyl, Beta -hydroxyethyl,-(CH2CH2O)3,5H, -(CH2CH2O)14-CH2CH2OH, benzyl, or forms together with R1a morpholine ring.
 11. Process according to claim 8 wherein R denotes aC8-C17alkyl or C18-alkenyl radical; A is -CONH-(CH2)3-; R1 is methyl;and R2 is -A-R, -(CH2)2-OOC-(CH2)16-CH3, methyl or Beta -hydroxyethyl.12. Process according to claim 8 wherein R denotes a C14-C18-alkylradical; A is -NH-CONH-(CH2)3-; and R1 and R2 are methyl.